CN109666039B - 一种五核锡（ii）化合物及其制备方法和应用 - Google Patents

一种五核锡（ii）化合物及其制备方法和应用 Download PDF

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CN109666039B
CN109666039B CN201811522499.7A CN201811522499A CN109666039B CN 109666039 B CN109666039 B CN 109666039B CN 201811522499 A CN201811522499 A CN 201811522499A CN 109666039 B CN109666039 B CN 109666039B
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周梅素
王迎迎
郭则灵
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Shanxi University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2284—Compounds with one or more Sn-N linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/42—Tin

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Abstract

本发明提供一种五核锡(II)化合物及其制备方法和应用。化合物合成步骤：在氮气保护下将三甲基硅基苯(基)氨基锂加入到反应容器中,加入乙醚溶解,在丙酮浴条件下加入二甲氨基腈，反应过夜,在丙酮浴条件下再加入SnCl2,慢慢升至室温，反应过夜，静置，过滤，滤液在真空下浓缩，室温下结晶，析出无色晶体，得五核锡(II)化合物；所述的三甲基硅基苯(基)氨基锂、二甲氨基腈和SnCl2的摩尔比为1:1:1‑1.25。该化合物可作为催化剂用于催化苯胺和N,N'‑二异丙基碳化二亚胺加成生成胍的反应，有较好的应用前景。

Description

一种五核锡（II）化合物及其制备方法和应用
技术领域
本发明涉及多核金属化合物，具体涉及基于二价锡离子和胍基配体构筑的一种五核锡 (II)化合物及其制备方法和应用。
背景技术
具有CN3结构的胍化合物作为一种有机碱能够催化Michael加成反应、Henry反应、亚磷酸酯与不饱和羰基化合物的加成和酯化反应，在制药、有机金属、配位化学以及有机合成等领域发挥着越来越重要的作用。
对称的具有功能基的取代胍在生物及制药工业上有着重要应用，其合成常采用胺和碳化二亚胺的催化加成得到。所使用的催化剂为半三明治夹心型的、桥联脒基、β-二亚胺或其类似的β-酮胺等配体支持的稀土金属催化剂。但催化剂合成所采用的稀土金属成本高，且合成过程较复杂。
发明内容
本发明的目的在于提供一种合成成本较低、方法简单的五核锡(II)化合物及其制备方法和应用。
本发明提供的一种五核锡化合物，是采用三甲基硅基苯(基)氨基锂为原料，和二甲氨基腈加成、与无水二氯化锡反应而得到，其化学结构式为：
Figure BDA0001903574230000011
本发明提供的一种五核锡(II)化合物的制备方法，包括如下步骤:
在氮气保护下将三甲基硅基苯(基)氨基锂加入到反应容器中,加入乙醚溶解,在丙酮浴条件下加入二甲氨基腈，反应过夜,在丙酮浴条件下再加入SnCl2,慢慢升至室温，反应过夜，静置，过滤，滤液在真空下浓缩，室温下结晶，析出无色晶体，得五核锡(II)化合物；所述的三甲基硅基苯(基)氨基锂、二甲氨基腈和SnCl2的摩尔比为1:1:1-1.25。
所述的三甲基硅基苯(基)氨基锂、二甲氨基腈和SnCl2的摩尔比优选为1:1:1.25。
本发明合成的五核锡(II)化合物能催化苯胺和N,N'-二异丙基碳化二亚胺加成生成胍的反应，可作为催化剂使用。
与现有技术相比本发明具有如下优点和效果：本发明五核锡(II)化合物采用金属有机及常规化学合成方法得到，化合物结构新颖，样品纯度高，稳定性好，合成成本低、方法简单。该发明构筑的五核锡(II)化合物能催化苯胺和N,N'-二异丙基碳化二亚胺的反应以高收率得到胍，可用作催化剂。
具体实施方式
实施例1：
五核锡(II)化合物a的制备：在氮气保护下将0.50g(2.92mmol)三甲基硅基苯(基)氨基锂加入到已称重的反应瓶中,加入30ml乙醚,在丙酮浴条件下加入二甲氨基腈(0.24ml,2.92mmol),反应过夜,在丙酮浴条件下再加入SnCl2(0.69g，3.65mmol),慢慢升至室温，反应过夜。静置，过滤，滤液在真空下浓缩，室温下结晶，析出无色晶体，得五核锡(II) 化合物a 0.256克,产率24.4％。
熔点：138-141℃
元素分析：理论值C,33.04；H,3.74；N,11.56％；实测值C,33.01；H,3.72；N,11.65。
核磁：1H NMR(CDCl3):δ1.69(THF),2.57(s,12H,N(CH3)2),3.21(s,12H,N(CH3)2),3.76 (THF),4.10(s,2H,NH),7.02-7.38(m,20H,Ph).13C NMR(CDCl3):δ25.61(THF),40.02,42.52 (N(CH3)2),68.00(THF),122.18(p-CPh),122.37(m-CPh),129.71(o-CPh),148.00(Cipso-Ph), 169.51(NCN)。
实施例2：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在25℃反应1.0h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率80.4％。
实施例3：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在25℃反应2.0h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率84.6％。
实施例4：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在60℃反应0.25h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率76.8％。
实施例5：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在60℃反应0.5h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率91.0％。
实施例6：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在80℃反应0.25h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率95.9％。
实施例7：
步骤1,五核锡(II)化合物a的制备同实施例1。
步骤2,苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.015g(0.01mmol)的化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.31mL(2.00mmol)和苯胺0.18mL(2.00mmol)。在80℃反应0.5h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率97.3％。

Claims (3)

1.一种五核锡(II)化合物，其特征在于，结构式为：
Figure FDA0002714808950000011
2.如权利要求1所述的一种五核锡(II)化合物的制备方法，其特征在于包括如下步骤:
在氮气保护下将三甲基硅基苯(基)氨基锂加入到反应容器中,加入乙醚溶解,在丙酮浴条件下加入二甲氨基腈，反应过夜,在丙酮浴条件下再加入SnCl2,慢慢升至室温，反应过夜，静置，过滤，滤液在真空下浓缩，室温下结晶，析出无色晶体，得五核锡(II)化合物；所述的三甲基硅基苯(基)氨基锂、二甲氨基腈和SnCl2的摩尔比为1:1:1.25。
3.如权利要求1所述的五核锡(II)化合物作为催化剂在催化苯胺和N,N'-二异丙基碳化二亚胺加成生成胍中的应用。
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